JPH01249187A - Method for purifying waste containing gallium and arsenic - Google Patents
Method for purifying waste containing gallium and arsenicInfo
- Publication number
- JPH01249187A JPH01249187A JP7685788A JP7685788A JPH01249187A JP H01249187 A JPH01249187 A JP H01249187A JP 7685788 A JP7685788 A JP 7685788A JP 7685788 A JP7685788 A JP 7685788A JP H01249187 A JPH01249187 A JP H01249187A
- Authority
- JP
- Japan
- Prior art keywords
- liq
- arsenic
- solid
- wastewater
- waste water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 27
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 12
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims description 24
- 238000000034 method Methods 0.000 title claims description 12
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims description 10
- 239000002699 waste material Substances 0.000 title 1
- 239000002351 wastewater Substances 0.000 claims abstract description 29
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 9
- 150000004679 hydroxides Chemical class 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000002244 precipitate Substances 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 229960004887 ferric hydroxide Drugs 0.000 abstract description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000006228 supernatant Substances 0.000 description 11
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 2
- 229910021513 gallium hydroxide Inorganic materials 0.000 description 2
- DNUARHPNFXVKEI-UHFFFAOYSA-K gallium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ga+3] DNUARHPNFXVKEI-UHFFFAOYSA-K 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、半導体製造工場等から排出される研磨廃水等
、ガリウム及び砒素を含む廃水の浄化処理方法に関する
。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for purifying wastewater containing gallium and arsenic, such as polishing wastewater discharged from semiconductor manufacturing factories and the like.
半導体製造工場等からは、ガリウム及び砒素を含む廃水
が排出される。このうち、特に砒素については、有害物
質としてその排出が厳しく規制されている。また、排出
先が農業用水の場合には、他の塩類も除去しなければな
らないため、廃水を系外に排出させないクローズドシス
テムを採ることが多くなってきている。Semiconductor manufacturing factories and the like discharge wastewater containing gallium and arsenic. Among these, arsenic in particular is a hazardous substance whose emission is strictly regulated. Furthermore, when the wastewater is used for agricultural purposes, other salts must also be removed, so closed systems are increasingly being used to prevent wastewater from being discharged outside the system.
従来、この種の廃水を処理するには、廃水に塩化第二鉄
を添加し、その後、ｐＨを中性付近に調整して水酸化鉄
を生成させ、砒素を共沈により除去した後、処理水を必
要に応じて塩類や有機汚染物を除去するため蒸発処理す
る方法が採用されている。Conventionally, to treat this type of wastewater, ferric chloride is added to the wastewater, the pH is then adjusted to near neutrality to produce iron hydroxide, arsenic is removed by coprecipitation, and then treatment is performed. Evaporative treatment of water is employed to remove salts and organic contaminants as necessary.
しかしながら、前記の方法では、処理水中の砒素を環境
基準の０．０５■／！以下にするのに、原水の砒素濃度
によって若干具なるが、Ｆｅ１度が廃水中に含まれる砒
素濃度に対して１０倍以上となるように塩化第二鉄を添
加する必要がある。そのため、金属スラッジが多量に発
生する欠点があり、この種の廃水の処理における課題で
あった。However, with the above method, the arsenic in the treated water is reduced to 0.05 μ/l, which is the environmental standard! In order to achieve the following, it is necessary to add ferric chloride so that the Fe 1 degree is 10 times or more the arsenic concentration contained in the wastewater, although this depends somewhat on the arsenic concentration of the raw water. Therefore, there is a drawback that a large amount of metal sludge is generated, which has been a problem in the treatment of this type of wastewater.
本発明は、前記従来技術の欠点を解消し、簡単な操作で
砒素を効率よく除去できるとともに、第二鉄塩の添加量
を節約し、発生スラッジ量を低減できる廃水の浄化処理
方法を提供することを課題とする。The present invention eliminates the drawbacks of the prior art and provides a wastewater purification method that can efficiently remove arsenic with simple operations, save the amount of ferric salt added, and reduce the amount of sludge generated. That is the issue.
本発明は、廃水を第二鉄塩で処理する前に、ｐＨ３〜５
に調整することによって廃水中のガリウムを水酸化ガリ
ウムとし、砒素を共沈させ、これを除去することによっ
て前記の課題を解決したものである。The present invention provides that the wastewater has a pH of 3 to 5 before being treated with ferric salts.
The above problem was solved by adjusting the gallium in the wastewater to gallium hydroxide, co-precipitating arsenic, and removing this.
すなわち、本発明による、ガリウム及び砒素を含む廃水
の浄化処理方法は、ガリウム及び砒素を含む廃水をｐＨ
３〜５に調整し、次いで、固液分離後、処理水に第二鉄
塩を添加し、アルカリ剤を添加してｐＨ６〜８に調整し
、固液分離することを特徴とする。That is, in the method for purifying wastewater containing gallium and arsenic according to the present invention, the wastewater containing gallium and arsenic is
3 to 5, and then, after solid-liquid separation, a ferric salt is added to the treated water, an alkali agent is added to adjust the pH to 6-8, and solid-liquid separation is performed.
本発明方法により、ガリウム及び砒素を含む廃水をｐＨ
３〜５に調整した後、固液分離することにより砒素は約
７０％以上除去される。これは、ｐＨ３〜５に調整する
ことにより廃水中に溶存していたガリウム等の金属が水
酸化物となり、これが凝集剤として作用し、砒素を共沈
させるためと考えられる。By the method of the present invention, wastewater containing gallium and arsenic can be adjusted to pH
After adjusting to 3 to 5, about 70% or more of arsenic is removed by solid-liquid separation. This is thought to be because metals such as gallium dissolved in the wastewater become hydroxides by adjusting the pH to 3 to 5, which act as a flocculant and co-precipitate arsenic.
本発明方法においては、この固液分離後の廃水に第二鉄
塩を添加する。ここで使用しうる第二鉄塩としては、塩
化第二鉄、硫酸第二鉄等が挙げられる。第二鉄塩は、Ｆ
ｅ／Ａｓの比が２〜６、好ましくは４〜５となるように
添加すればよい。In the method of the present invention, a ferric salt is added to the wastewater after solid-liquid separation. Examples of ferric salts that can be used here include ferric chloride and ferric sulfate. Ferric salt is F
It may be added so that the e/As ratio is 2 to 6, preferably 4 to 5.
このように第二鉄塩を添加した後、充分に撹拌し、次い
で、アルカリ剤、例えば水酸化ナトリウム、水酸化カリ
ウム等を添加してｐＨ６〜８に調整する。これにより、
先に添加した第二鉄塩が水酸化第二鉄を形成し、これが
凝集剤として作用し、砒素を共沈させる。この際生成す
る沈殿を固液分離することにより得られる処理水の砒素
濃度は、極めて低く、容易に規制値以下にすることがで
きる。After adding the ferric salt in this way, the mixture is thoroughly stirred, and then an alkaline agent such as sodium hydroxide, potassium hydroxide, etc. is added to adjust the pH to 6 to 8. This results in
The ferric salt added earlier forms ferric hydroxide, which acts as a flocculant and coprecipitates the arsenic. The arsenic concentration of the treated water obtained by solid-liquid separation of the precipitate produced at this time is extremely low and can be easily reduced to below the regulatory value.
固液分離に当たって、凝集効果をさらに向上させるため
、必要に応じて常用の高分子凝集剤を添加してもよい。In order to further improve the flocculating effect during solid-liquid separation, a commonly used polymer flocculant may be added as necessary.
次に、実施例により本発明を説明するが、本発明はこれ
に限定されるものではない。Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto.
実施例Ｉ
Ｇａｐ度１４７ｍｇ／ｆ、Ａｓ濃度１７５ｍｇ／／！を
含むｐＨ８，６０の廃水を試料とした。この試料に硫酸
を添加してｐＨ３に調整した後、５分間撹拌した。３０
分静置後、得られた上澄水に塩化第二鉄を第１表に示す
ようにＦｅ添加量を変化させて加え、かきまぜ装置で１
０ Ｏｒｐｍで５分間撹拌した。Example I Gap degree 147 mg/f, As concentration 175 mg//! The sample was wastewater with a pH of 8.60. Sulfuric acid was added to this sample to adjust the pH to 3, followed by stirring for 5 minutes. 30
After standing still for 1 minute, ferric chloride was added to the supernatant water with varying amounts of Fe as shown in Table 1, and a stirrer was used to add ferric chloride to the supernatant water.
Stirred for 5 minutes at 0 Orpm.
次に、水酸化ナトリウムを添加してｐＨ７に調整した後
、１１００ｒｐで５分間、４０ｒｐｍ＋で１０分間撹拌
し、３０分静置後、得られた上澄水のＡｓ濃度を測定し
、結果を第１表に示す。Next, after adding sodium hydroxide and adjusting the pH to 7, the mixture was stirred at 1100 rpm for 5 minutes and at 40 rpm+ for 10 minutes, and after standing still for 30 minutes, the As concentration of the obtained supernatant water was measured, and the results were recorded in the first Shown in the table.
比較例１
廃水を始めにｐＨ３に調整しない以外は、実施例１と同
じ操作を行い、得られた上澄水のＡｓ？ａ度を測定し、
結果を第１表に示す。Comparative Example 1 The same operation as in Example 1 was performed except that the wastewater was not initially adjusted to pH 3, and the resulting supernatant water was As? Measure a degree,
The results are shown in Table 1.
第１表
上記の表から明らかなとおり、本発明によればｐＨ３に
調整後、固液分離することにより既に砒素の約７０％が
除去され、Ｆｅの添加量を約１／２に低減してＡｓ濃度
を０．０３■／２以下にすることができた。Table 1 As is clear from the above table, according to the present invention, approximately 70% of arsenic has already been removed by solid-liquid separation after adjustment to pH 3, and the amount of Fe added has been reduced to approximately 1/2. It was possible to reduce the As concentration to 0.03/2 or less.
実施例２
Ｇａ ：ａ度４８５ ｍｇ／ Ｌ Ａｓ濃度４３４■／
１を含む廃水を硫酸によりｐＨ３に調整した後、５分間
撹拌し、３０分静置した。得られた上澄水中の砒素濃度
は１２８■／ｌとなっていた。Example 2 Ga: A degree 485 mg/L As concentration 434■/
After adjusting the pH of the wastewater containing 1 to 3 with sulfuric acid, it was stirred for 5 minutes and left to stand for 30 minutes. The arsenic concentration in the supernatant water obtained was 128 μ/l.
この上澄水にＦｅ添加量を変化させて加え、実施例１と
同様に操作し、得られた上澄水のＡｓ濃度を測定し、結
果を第１図に示す。Varying amounts of Fe were added to this supernatant water, and the same procedure as in Example 1 was carried out, and the As concentration of the obtained supernatant water was measured. The results are shown in FIG.
比較例２
廃水を始めにｐＨ３に調整しない以外は、実施例２と同
じ操作を行い、得られた上澄水のＡｓ濃度を測定し、結
果を第２図に示す。Comparative Example 2 The same operation as in Example 2 was performed except that the wastewater was not initially adjusted to pH 3, and the As concentration of the resulting supernatant water was measured. The results are shown in FIG. 2.
実施例３
Ｇａ濃度２００ｍｇ／ｆ、Ａｓ濃度２００ｍｇ／ｆを含
む廃水を試料とした。この試料をｐＨ４に調整した後、
５分間撹拌した。３０分静置後、得られた上澄水に塩化
第二鉄をＦｅ／Ａｓ比１及び２になるように変化させて
加え、実施例１と同様に操作し、得られた上澄水のＡｓ
濃度を測定し、結果を第２表に示す。Example 3 Wastewater containing a Ga concentration of 200 mg/f and an As concentration of 200 mg/f was used as a sample. After adjusting this sample to pH 4,
Stir for 5 minutes. After standing still for 30 minutes, ferric chloride was added to the obtained supernatant water at varying Fe/As ratios of 1 and 2, and the same procedure as in Example 1 was carried out to increase the As content of the obtained supernatant water.
The concentration was measured and the results are shown in Table 2.
比較例３
廃水を始めにｐＨ３に調整しない以外は、実施例３と同
じ操作を行い、得られた上澄水のＡｓ濃度を測定し、結
果を第２表に示す。Comparative Example 3 The same operation as in Example 3 was performed except that the wastewater was not initially adjusted to pH 3, and the As concentration of the resulting supernatant water was measured. The results are shown in Table 2.
第２表
第２表から明らかなとおり、ｐＨ４に調節後に固液分離
すると、水酸化ガリウムが生成し、その共沈作用により
大部分の砒素が除去され、その後、第二鉄塩で処理する
ことにより、砒素を極めて微量まで除去することができ
る。Table 2 As is clear from Table 2, when solid-liquid separation is performed after adjusting the pH to 4, gallium hydroxide is produced, and most of the arsenic is removed by its coprecipitation action, and then treated with ferric salt. By this method, arsenic can be removed to extremely small amounts.
本発明方法によれば、第二鉄塩の添加量を著しく低減し
て、簡単な操作で砒素を極めて微量まで除去することが
でき、発生スラッジ量を著しく低減することができる。According to the method of the present invention, the amount of ferric salt added can be significantly reduced, arsenic can be removed to an extremely small amount with simple operations, and the amount of generated sludge can be significantly reduced.
第１図は、実施例２における第二鉄塩の添加量（Ｆ ｅ
／ Ａ ｓ比）と処理水のＡｓ濃度の関係を示すグラ
フ、第２図は比較例２における第二鉄塩の添加量（Ｆｅ
／Ａｓ比）と処理水のＡｓ濃度の関係を示すグラフであ
る。Figure 1 shows the amount of ferric salt added in Example 2 (F e
Figure 2 is a graph showing the relationship between the As concentration in the treated water and the As concentration in the treated water.
2 is a graph showing the relationship between the As concentration in the treated water and the As concentration in the treated water.
Claims (1)
、次いで、固液分離後、処理水に第二鉄塩を添加し、ア
ルカリ剤を添加してｐＨ６〜８に調整し、固液分離する
ことを特徴とするガリウム及び砒素を含む廃水の浄化処
理方法。1. Adjust wastewater containing gallium and arsenic to pH 3 to 5, then solid-liquid separation, add ferric salt to the treated water, add an alkali agent to adjust pH to 6-8, and solid-liquid separation. A method for purifying wastewater containing gallium and arsenic.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7685788A JPH01249187A (en) | 1988-03-30 | 1988-03-30 | Method for purifying waste containing gallium and arsenic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7685788A JPH01249187A (en) | 1988-03-30 | 1988-03-30 | Method for purifying waste containing gallium and arsenic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01249187A true JPH01249187A (en) | 1989-10-04 |
| JPH0461712B2 JPH0461712B2 (en) | 1992-10-01 |
Family
ID=13617322
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7685788A Granted JPH01249187A (en) | 1988-03-30 | 1988-03-30 | Method for purifying waste containing gallium and arsenic |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01249187A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002172395A (en) * | 2000-12-05 | 2002-06-18 | Nec Environment Eng Ltd | Method for iron hydroxide flocculation and sedimentation treatment of thick inorganic component- containing wastewater |
| JP2002320979A (en) * | 2001-04-27 | 2002-11-05 | Sharp Corp | Method and system for treating metal-containing drainage |
| JP2003001269A (en) * | 2001-06-19 | 2003-01-07 | Kurita Water Ind Ltd | Equipment for treatment of waste water containing gallium |
| JP2003001275A (en) * | 2001-06-19 | 2003-01-07 | Kurita Water Ind Ltd | Equipment for treatment of waste water containing gallium-arsenic |
-
1988
- 1988-03-30 JP JP7685788A patent/JPH01249187A/en active Granted
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002172395A (en) * | 2000-12-05 | 2002-06-18 | Nec Environment Eng Ltd | Method for iron hydroxide flocculation and sedimentation treatment of thick inorganic component- containing wastewater |
| JP2002320979A (en) * | 2001-04-27 | 2002-11-05 | Sharp Corp | Method and system for treating metal-containing drainage |
| US7294268B2 (en) | 2001-04-27 | 2007-11-13 | Sharp Kabushiki Kaisha | Metal containing waste water treatment method and metal containing waste water treatment equipment |
| JP2003001269A (en) * | 2001-06-19 | 2003-01-07 | Kurita Water Ind Ltd | Equipment for treatment of waste water containing gallium |
| JP2003001275A (en) * | 2001-06-19 | 2003-01-07 | Kurita Water Ind Ltd | Equipment for treatment of waste water containing gallium-arsenic |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0461712B2 (en) | 1992-10-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |